Bis-chlorobutenyl sulfides



Patented July 22, 1952 i BIS-CHLOROBUTENYL sULFinEs we 'Warren D. Niederhauser, Philadelphia; Pa'i, as-

' signor to Robin & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application January 26, 1950,

- g .Serial-No. 140,749

3 Claims. (Cl. 260609) UNITED. STATES PATENT ori ce This invention relates to bis-chlorobutenyl esters or alkyd resins. Or, the mixture of isosulfides having the formulas meric products of this invention can be readily n converted into a mixture of isomeric diamines C1CH2CH VHCH2 s CH2CH*CHCH2C1 which can be reacted with dicarboxylic acids and 5 including the one described above to form poly- CHZ:cH CHCI CHZ S CH2CHCICHZCH2 amides. Thus the compounds of this invention serve as the source of dicarboxylic acids, glycols These new compounds which are also propand diamines which are the chief materials used erly identified respectively as bis(4-chloro-2buin the formation of polyesters and polyamides. e y fid a d bis( -h.l0r03-but The following example serves to illustrate the are prepared s1multaneously as a mixture of isopreferred th d of preparing the products of mers by the reaction of one mole of sulfur dithis invention, chloride, SO12, with two moles of 1,3-butadiene. Example The reaction takes the following courses:

SO12 2CH2=CH CH=CH2 15 A flask, equipped with thermometer, agitator,

reflux condenser, dropping funnel and inlet tube,

I was first charged with 360 parts of carbon tetrachloride which served as a solvent for the subc1cH2cH=cHoH2-s-cH20H=oH oH2o1 sequent reaction mixture. This solvent was agiand tated and 216 parts of LS-butadiene and 103 parts of sulfur d1ch1oride were added slowly and CH2:CH-CHClCI-I2SCH2CHClCI-IzCI-Ia simultaneously to the solvent over a period of one The two reactants combine quite readily even hour while the temperature was maintained at in the absence of a catalyst at temperatures ig g gi gi gggi ggfi i gg ggg gg fig g from 0 C. to about 50 C. although the pre- 9 g ferred temperatures are frm about 10 C to was discontinued and the mixture was allowed a I to stand at room temperature for 15 hours. The

3223 53 5:5 gg' figz fi g ggg gi i g? solvent and uncombined reactants were then sures up to about 100 pounds per square inch are $13,2 3,25 gzgi gg 1 :2: fi g ii fig gfii satisfactory. Although the butadiene and sulfur residue which had a viscosity at 005 dichloride react in the ratio of two molar equivapoisa This residue was distilled at 3 mm of it is apparent that an excess of either can be fifif gfifii $32 2 g g g ggs ggg igz n s empbyei, Actllauy it is nluch prferred have tilled. Practically all of it boiled at 118 c.-122" the butadiene 1n excess since this reduces the 0 C. and 3 pres-sure and the product was a highly chlorinated by-products. The use of solvents is recommended and for this purpose car- Obuteny1 sulfide-s had denslty of index of refract1on of 1.5280, a molar refrac bon tetrachtonde t partlculafly sat1sfactry' *0 tivity of 56.00 as against a calculated value of simultaneously can be separated by fractmnal calculated value for (C4H6C1) 23 of 211 The redistillation, but for many purposes the separasums of analysis were as follows. C1'2:33 tion is not necessary. For example, the mixture s:14 6% iodine number=233 as aainst isomers on reacting with an inorganic lowing calculated values: Cl2=33.6%; S=15.2%;

anide appears to yield only one dinitrile, presumably due to allylic rearrangement. This dig gf gf v nitrile is then readily hydrolyzed to a dicarbox- L As a'new composition of matter a mixture ylic acid which is very useful for the manufacture of alkyd resins. Alternatively the original gfi g i z gi bis chlorobutenyl sulfides having of an alkali carbonate to produce a mixture of ClCI-IaCH:CHCHzSCl-IzCH=CI-ICI-Iz0l and J .,I .il' described immediately above to form linear poly- ,CI-Iz=CHCHClCH2-S-CI-I2CHC1CI-I=CH= 3 a 2. A process for preparing a mixture of the which comprises chemically combining two molar isomeric bis-chlorobutenyl sulfides having the equivalent weights of 1,3-butadiene and one formulas molar equivalent weight of sulfur dichloride at p a temperature from 10 C. to 30 C. C1CH2CH CHCH2-S-CH2CH -CHCH2C1 5 WARREN D NIEDERHAUSER. and

:cncirmcwcmcnercrmcm REFERENCES-P CITED "The following-referencesare of "record in the which comprises chemically combining two molar equivalent weights of 1,3-butadiene and one file of ggfzg' PATENTS molar equivalent weight of sulfur dichloride at a temperature from 0 C. to 50 C.- --Number- Name Date 3. A process for preparing ammixture of Ythe 2422; 12 715 Winning et al June 1'7, 194'! j isomeric bis-chlorobutenyl,,-sulfides having; the 1 2,451,113 Watkins Apr. 19, 1949 formulas 115- "OTHER REFERENCES C1CH2CH=CHCHPs-CH26H;GHCH2C1* Backer=et--al., Recueill des Travaux Chimiques and *(French) Tome 54 (1935). pp 52-56. 

1. AS A NEW COMPOSITION OF MATTER A MIXTURE OF THE ISOMERIC BIS-CHLOROBUTENYL SULFIDES HAVING THE FORMULAS 